CN104822641B - For the bag of multi-component adhesive system - Google Patents
For the bag of multi-component adhesive system Download PDFInfo
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- CN104822641B CN104822641B CN201380062470.4A CN201380062470A CN104822641B CN 104822641 B CN104822641 B CN 104822641B CN 201380062470 A CN201380062470 A CN 201380062470A CN 104822641 B CN104822641 B CN 104822641B
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- addition polymerization
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
- B65D81/3261—Flexible containers having several compartments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
- B65D77/003—Articles enclosed in rigid or semi-rigid containers, the whole being wrapped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
- B65D77/22—Details
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
- C04B40/0641—Mechanical separation of ingredients, e.g. accelerator in breakable microcapsules
- C04B40/065—Two or more component mortars
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
- C04B40/0666—Chemical plugs based on hydraulic hardening materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1067—Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Mechanical Engineering (AREA)
- Analytical Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Epoxy Resins (AREA)
Abstract
Disclose the bag for multi-component adhesive,It has (I) resin Composition,It includes (a) at least one radical polymerizable compound,(b) at least one compound polymerizable by addition polymerization,(c) accelerator,Optionally,D () inhibitor and (e) have the compound of Liang Ge functional groups,Wherein,One functional group can be with free radical (co) polymerization and another functional group can be by addition polymerization (co) polymerization,And (II) curing agent component,It includes (A) at least one curing agent for addition polymerization and (B) at least one radical initiator,Wherein the bag includes Part I A1,Its at least three single component for including multi-component adhesive,With Part II A2,Its at least two single component for including multi-component adhesive,Wherein the single component of multi-component adhesive can so be divided into two parts A1 and A2,So that preventing the solidification only generation after single component all mixing of the reaction and adhesive between single component.So that the storage-stable of component is possibly realized.
Description
Bag the present invention relates to be used to preserve the multi-component adhesive component for being separated from each other storage, more particularly to for preserving
The bag of three components of the plaster system based on dual cure adhesive.
For a long time, the reaction resin material based on unsaturated polyester resin, vinyl ester resin or epoxy resin is made
It for the adhesive and adhesive of chemical fastening techniques is known to be.This herein relates to bicomponent system, one of component
Curing agent is included comprising reaction resin and another component.Other conventional constituents, such as filler, accelerator, stabilizer, solvent
Can be included in one and/or described another component including reactive solvents (reactive diluent).So, lead to
Cross and mix both components and initiation reaction and form cured product.
Generally, multi-component masses, for example for example, putty material, foamed material and encapsulant come for user
Saying can provide in the paper tinsel bag as bi-component or multi-component material in cylinder, box and as injection system.Paper tinsel bag has confirmed work
It is the bag for these materials, particularly compared with box, it is characterised in that low using the material share that must be abandoned after material.
Additionally, paper tinsel bag simply and can be manufactured cost-effectively.
In principle, two kinds of systems are used in chemical fastening techniques：It is a kind of based on free radical is polymerizable, olefinic unsaturated
Compound, it generally uses peroxide cure, and a kind of based on epoxide-amine system.The first system is characterised by
Quickly solidification, particularly at low temperature such as -10 DEG C, but it has weakness in terms of load value.In contrast, epoxidation
Thing-amine system has slower curing rate, but the robustness of load value and system aspect is favourable.
In order to merge two kinds of advantages of system, research is developed to develop double solidification adhesives.It means that it is solid
The system that change is carried out in free radical mode and by addition polymerization.These systems are also referred to as mixed system or mixed adhesive.
These mixed systems are typically based on resin combination, and it includes the compound that can solidify according to the first reaction type, for example
With the compound of radical polymerization, and can be solidified according to second reaction type different from the first reaction type
Compound, such as by the compound that addition polymerization is polymerizable, such as epoxides.This resin combination can based on free radical
The compound of polymerization and the epoxides that can be for example solidified with peroxide and amine.
Formerly such system is not described in disclosed application EP1021532.
But be also known that except comprising free radical polymerizable moiety, also comprising causing polyurethane or polyureas, such as base
In interpenetrating polymer networks (IPN) part of polymethacrylates and polyurethane system as adhesive etc..
Conventional bi-component is separated as follows so that comprising reactive compounds and optionally other additives and filler, example
Such as reactive diluent, inhibitor, accelerator, thickener, the resin Composition of thixotropic agent and inorganic filler, and comprising curing agent
The curing agent component of optionally other additives and filler, such as thickener, thixotropic agent, tackifier and inorganic filler is in space
Upper separately packaging so that only just reacted when two kinds of components are mutually mixed.In paper tinsel bag is used as the situation of packaging, resin group
Subpackage is in the first paper tinsel bag, and resin Composition is packaged in the second paper tinsel bag spatially separated with the first paper tinsel bag.This with
The situation of the cylinder for also using is similar to, wherein equally having used less comprising solid in the larger box comprising resin Composition
The cylinder of agent component.In situation of the box as packaging, this generally comprises two separate rooms, to realize the space point of component
Open.
For mixed adhesive, as described in application EP10153243, it is wrapped in conventional double bag injection systems
Containing the resin Composition being contained in bag film, the curable compound of free radical, the compound that can be solidified with amine, catalyst promotees
Enter agent, optionally, reactive diluent, inhibitor and the compound for forming bridge.So curing agent component will comprising this two
Plant curing agent：Peroxide and amine.
However, this generates some problems.In terms of curing agent, problem is that only a small amount of peroxide and amine can be with short
The combination of phase storage-stable ground, i.e., do not have flexibility, particularly for the amine hardener of epoxy resin in terms of selection.Additionally, not
Fully ensure enough storage stabilities, or even in the case of those curing agent that can be mutually combined.This necessarily causes
The bonding strength of the detraction of unpredictable curing agent and binder performance, i.e. anchoring element.
However, in terms of resin, problem is it is expected that the reaction each other of single component.
Delayed free base polymerization compound be commonly added in resin or resin Composition so as to make its stable storing and/or
Regulation gel time.4- hydroxyls -2,2,6,6- tetramethyl piperidine -1- epoxides (Tempol) is chemical combination that is conventional and being proved
Thing.Document (such as Sheldon et al., Org.Biomol.Chem., 2003,1,3232；E.G.Rozantsev et al.,
Russ.Chem.Rev., 1971,40 (3), 233) indicate, Tempol with wherein be used as catalyst be used for peroxide firming agent
The Cu (I) and Cu (II) reactant salt of activation, especially in the presence of aerial oxygen.For other stable nitroxyls certainly
This decomposition reaction has been also assumed that by base.
Therefore, in the situation of the construction of the bag for mixed adhesive, in particular according to the situation of EP10153243 in,
It is noted that following components can not be mutually mixed, so as to negatively affect the property of storage stability or hardening time and adhesive
Energy：
- peroxide and amine,
- Tempol and transition metal promoter
- peroxide and radical polymerizable compound,
- amine and epoxide, and
- radical polymerizable compound and amine.
On bag, single component must also be separated so as to the ratio of required amount, particularly applied adhesives when
Between the mixing ratio of curable compound and curing agent is kept on point, such as on the time point for extruding single component.
Used for original position, it means that resin combination, peroxide firming agent, amine hardener, and accelerator must
Must be spatially so arranged apart so that the reaction being not intended to, i.e., the solidification of resin combination as described above or other groups
The inactivation for dividing all is inhibited by each other.Present difficulty is present in so packaging multicomponent, double curing adhesive (hybrid bondings
Agent) so that prevent the reaction each other of single component, and adhesive to be easy to original position and use, such as in conventional glass or
In plastic barrel or it is generally employed for the pressurizing unit of two component adhesive.This bag is currently unknown.
However, even in for example producing polyurethane or polyureas to replace the mixed adhesive of Epoxy-amine System with system,
Single component can not be arbitrarily miscible, is equally necessary especially for the system amine with polyureas.
Therefore, it is an object of the invention to provide the bag for multi-component adhesive system, particularly referred to for introductory song
The mixed adhesive of species, its can storage-stable, can be used in the conventional pressing device for having used, and keep needed for
The curable compound and the mixing ratio of curing agent wanted.
The purpose is realized by bag according to claim 1.Preferred embodiment is illustrated in the dependent claims.
An advantage of the invention that, peroxide cure and a kind of resin can be used based on a kind of resin Composition using
In the situation of the mixed adhesive that component can be solidified with amine, it is possible to use any peroxide and any amine, to prepare this
Very big flexibility is kept in the case of two kinds of curing systems and the free radical scavenger of any amount can be selected, so as to
Individually freely adjust gel time as needed.
Additionally, the present invention also causes to use the peroxide of more absolute magnitudes, and it is no more than 1 weight based on curing agent component
The statutory restrictions value for measuring the peroxide share of % is possibly realized.Therefore, in the situation of the peroxide or even in absolute magnitude high,
Optionally, the bag no longer marks " inflammable ", and this causes user's acceptance higher.
Other advantages of the invention are, with the conventional bicomponent based on free radical curable resin and based on epoxy resin
System is compared, and tackifier (epoxy resin is used as tackifier) are mixed into curing agent component (peroxide) for increasing wherein
Allow to omit extra addition tackifier in the situation of storage stability, because these tackifier can weaken the machine of curing materials
Tool property, and generally it is classified to environmental hazard.
In the sense of the present invention, " mixed adhesive " or " dual cure adhesive " is represented comprising can based on free radical
Polymerizable compound and the curing agent for radical polymerization, the curing agent mixture of radical initiator, and based on by addition
The compound of polymerizing polymerizable and for addition polymerization curing agent resin compound adhesive composition.Both trees
The single component of lipoprotein mixture, i.e. radical polymerizable compound, by the compound that addition polymerization is polymerizable, curing agent promotees
Enter agent, inhibitor, optionally, the compound for bridging (has a compound of Liang Ge functional groups, one of functional group can be with
Radical polymerization and another functional group can be with addition polymerization), reactive diluent, additive, and filler is of the invention
In meaning referred to as " single component ".Additionally, " stabilizer " is to slow down, suppress or prevent curing reaction, particularly radical polymerization
The compound of conjunction, but wherein the compound becomes stable storing solid with the radical polymerizable compound of resin compound
The amount addition of gel time is not damaged during change.On the other hand, " inhibitor " is to slow down, suppress or prevent curing reaction, especially
It is the compound of radical polymerization, wherein, however, compared with the solidification mixture without inhibitor, it coagulating during curing
The amount of glue time lengthening is added in radical polymerizable compound.Therefore, compound can be both stabilizer and inhibitor.
However, it is also possible to use different compounds.
Subject of the present invention is the bag for multi-component adhesive, and it includes (i) resin Composition, and it has (a) at least
A kind of radical polymerizable compound, (b) at least one compound being polymerized by addition polymerization, (c) accelerator, optionally,
D () at least one inhibitor and optionally (e) at least one compound with Liang Ge functional groups, one of functional group can be with
Free radical (co) polymerization and another functional group can be by addition polymerization (co) polymerizations, and (ii) curing agent component, its tool
There are (A) at least one curing agent for addition polymerization and (B) at least one radical initiator, it is characterised in that comprising many
At least three kinds Part I A1 of single component of component adhesives, and at least two single components comprising multi-component adhesive
Part II A2, wherein the single component of multi-component adhesive so distribution in two parts A1 and A2 so that only complete
Mix entirely after single component and adhesive solidification just occurs and the premature reaction between single component is prevented from.
Two parts A1 and A2 of the bag can be structured as the subregion of separated container, wherein by separating
Wall and similar mode are separated, or are arranged in the second dependent container in the first container, or as the space of dependent
Separate container.
According to the present invention, the compound with carbon-to-carbon triple bond well known by persons skilled in the art, olefinic unsaturation chemical combination
Thing, cyclic monomer and mercaptan-alkynes/alkene (Thio-Yne/Ene) resin are suitable as radical polymerizable compound.
In these compounds, preferred alefinically unsaturated compounds, it includes Styrene and its derivatives, (methyl) propylene
Acid esters, vinyl esters, unsaturated polyester (UP), vinyl ethers, allyl ether, itaconate, bicyclopentadiene compound and unsaturation
Fat, wherein unsaturated polyester resin and vinyl ester resin are specially suitable, and for example in application EP 1 935 860
It is described in the A1 of A1, DE 195 31 649 and the A1 of WO 10/108939.Here, vinyl ester resin is most preferred,
Because their hydrolytic stability and outstanding engineering properties.
In the sense of the present invention, vinyl ester resin is the oligomer with least one (methyl) acrylate end groups
Or polymer, so-called (methyl) acrylate functional resin；It also includes carbamate (methyl) acrylate
With epoxy radicals (methyl) acrylate.
Vinyl ester resin, it only has unsaturated group in terminal position, such as by epoxides oligomer or poly-
Compound (such as bisphenol-A-diglycidyl ether, the epoxides of phenol-novolac type, or the epoxy based on tetrabromobisphenol A
Compound oligomer) obtained with the reaction of such as (methyl) acrylic acid or (methyl) acrylamide.Preferred vinyl ester resin is
The resin of (methyl) acrylate functional and by epoxides oligomer or polymer and methacrylic acid or metering system
Acid amides, the preferably reaction with methacrylic acid are obtained.The example of such compound can be by applying for US 32977345 A, US
3772404 4618658 A, GB 2217722A1, DE 3744390 known to the A1 and A1 of DE 4131457 of A, US.
Free radical starting material usually used and well known by persons skilled in the art can serve as radical initiator.Can be with
The compound for triggering polymerization at room temperature is preferred, and peroxide radical initiator is particularly preferred.
Compound usually used and well known by persons skilled in the art is suitable as by the polymerizable chemical combination of addition polymerization
Thing.It is exemplary to refer to, epoxy resin, isocyanates, 'beta '-ketoester, such as acetoacetate, cyclic carbonate ester and alkene, i.e. electron deficient carbon-
Carbon double bond, wherein compound can have at least one, preferably two or more functional groups, i.e. epoxy radicals, isocyanates
Base, acetoacetyl and alkenyl.It is preferred that epoxide, and more preferably per molecule has the epoxidation of at least two epoxide groups
Compound.Accordingly, comprising active hydrogen atom and be not curing agent that ionic compound can serve as addition polymerization.Show
Example property ground is it can be mentioned that amine, alcohol and mercaptan, wherein compound per molecule can have at least one, preferably two or more ammonia
Base-, sulfenyl-or oh group.Amine is preferred and amine of the per molecule with least two amino groups is preferred.
If vinyl compound is used as by the polymerizable compound of addition polymerization, then radical polymerization and addition are poly-
Conjunction can be carried out with parallel, if vinyl compound is electrophilic enough.This has the advantage that must use only one kindization
Compound is as resin Composition and therefore expected difficult less in the case where this kind of mixed adhesive is produced.
The characteristic and phase of mixed adhesive can be influenceed by the compound of addition polymerization polymerization by selection
The regulation answered is used for desired purposes.
In a preferred embodiment of the present invention, it is epoxide and corresponding by the polymerizable compound of addition polymerization
Curing agent (A) be amine.The compound with Liang Ge functional groups is included for mixed adhesive, one of functional group can be certainly
By base (co) polymerization and another functional group can be by the situation of the compound of addition polymerization (co) polymerization, can be by addition
The functional group for being polymerized and being polymerized is epoxide group.
Compound usually used and well known by persons skilled in the art can serve as accelerator and inhibitor, depending on hybrid bonding
Depending on the application field of agent.Suitable accelerator is for example, amine, preferred tertiary amine and/or slaine.For example, being generally used for freedom
The inhibitor of base polymerizable compound, such as phenols and non-phenolic compounds, such as stable free radical, for example
Galvinoxyl- and N- epoxides free radical and/or phenthazine are suitable inhibitor.
For the application in technique for fixing field, such as reacting resin plaster, on single component application reference
Compound described in EP10153243, its content is thus incorporated into the application.
It is preferred that Part I A1 includes the polymerizable compound of (a) at least one free radical, (c) at least one accelerator,
(A) at least one tool of at least one curing agent for addition polymerization, optionally (d) at least one inhibitor and optionally (e)
The compound of You Liangge functional groups, one of functional group can be with free radical (co) polymerization, and another functional group can pass through
Addition polymerization (co) polymerization.Therefore, (A) is separated from each other storage for the curing agent and (B) radical initiator of addition polymerization, and
And multi-component adhesive is not limited to radical initiator such as peroxide and the curing agent such as amine for addition polymerization
Specifically, nonreactive combination each other, and the single component for being not limited to particular amount.Thus reach, corresponding to desired
Adhesive properties, any radical initiator and any curing agent may be used to addition polymerization.For the solidification of addition polymerization
Agent and for radical initiator can as multiple compounds mixture exist.Accordingly, in the preparation of curing agent
Ensure that more flexibilities.
Part II A2 is accordingly comprising (b) at least one compound polymerizable by addition polymerization and (B) at least
Plant radical initiator.In the situation comprising peroxide as the epoxide-amine-matrix system of radical initiator, can
Thus to reach peroxide thickening, this produces positive effect to storage stability.Because epoxide has than amine more
Therefore big volume, can reach and pack the peroxide and peroxide share of more absolute magnitudes less than must identify
1% amount so that at least with the no longer necessary mark of peroxide.This causes bigger Consumer acceptance.
It is preferred that at least 3 kinds single components (a) of multi-component adhesive, (c) and (A) and if there is (d) and (e) exist
There is provided in Part I A1 in separate room, further separately stored to obtain the single component of reacting to each other property.
The room can be configured to the subregion of container or separate, spatially separate container, be similar to
In such in part.
It is verified herein that single component advantageously will be so separated in Part I A1 so that the first Room K1 is included
(a) at least one radical polymerizable compound and optionally (d) at least one inhibitor and optionally (e) at least one tool
The compound of You Liangge functional groups, one of functional group can with free radical (co) polymerization and another functional group can by plus
Into polymerization (co) polymerization, and second Room K2 (A) includes at least one curing agent for addition polymerization and (c) at least one rush
Enter agent.Therefore, if there is inhibitor, the reaction between accelerator (c) and inhibitor (d) will no longer be possible to so that can keep away
Exempt from the adverse effect in terms of the storage stability from reaction, and gel-time drift related to this.Additionally, may be used also
To use accelerator incompatible each other and inhibitor.
For example, slaine, such as Cu (II) salt can serve as the nitroxyl free radical of accelerator and stabilization, for example
Tempol can serve as the inhibitor in multi-component adhesive, without causing nitroxyl free radical to be decomposed by slaine.Made
The concentration of nitroxyl free radical is variable, so that the gel time of radically curing component can correspond to mixing
The requirement of curing agent is freely adjusted.Additionally, instead of nitroxyl free radical or in addition to the free group of nitroxyl, can also make
Other inhibitor are used, for example they are not compatible with Cu (II) salt, such as phenol or catechol.
Other advantages are can be poly- for addition by merging (c) accelerator (such as Cu (II) naphthoate) and (A)
The curing agent (such as amine) of conjunction realizes the extra pre-activate of accelerator.Other parts can also be dissolved in (A) poly- for addition
In the curing agent (such as amine) of conjunction, it has activated accelerator, such as Cu (II) salt.
In a preferred embodiment of the present invention, Part I A1, particularly the first Room K1 are further comprising at least more than
A kind of reactive diluent for radical polymerizable compound.Thus, it is possible to gluing radical polymerizable compound
Desired value is arrived in degree regulation.
The mixing ratio A1 of Part I and Part II:On the one hand A2 depends on the component for using, and on the other hand takes
Certainly in application field, wherein bag of the invention should have been used.Can be 1:1 to 10:1 section, preferably 3:1 to 7:1 scope
Interior tune.In technique for fixing field, it has proved that for mixed adhesive as the big of the plaster material for the fixed purpose of chemistry
For majority application, mixing ratio A1 is adjusted:A2 is 3:1 or 5:1 is favourable.
If providing the mixing ratio of the first Room K1 and second Room K2, the first Room K1 and second Room K2 in Part I A1
Favourable is 4:1 to 1:4, specifically for 4:1 to 1:1.
Bag of the invention is comprising many frees degree to adjust mixing ratio A1 just:A2 and K1:K2.However, amine
HAV values (amine equivalent weight) using epoxide-amine-system as the situation by the polymerizable compound of addition polymerization
In there is maximum influence to two ratios.By amine of the selection with HAV values higher, the share of second Room K2 can be increased,
It is with so that ratio A1:A2 can in a varying manner include (A) amine and (c) accelerator.But, with amine reactive compound and amine
Ratio and radical polymerizable compound and the reactivity curing agent with amine comparison mixing ratio A1:A2 and K1:K2 has
Influence.
In especially preferred embodiment of present invention, three component bags are that have comprising multi-component adhesive at least three
Single component the first paper tinsel bag Fb1, and at least two single components comprising multi-component adhesive the second paper tinsel bag Fb2 paper tinsel
Bag, wherein the single component of multi-component adhesive is so distributed in two bag films Fb1 and Fb2 so that the solidification of adhesive
Only just occur after single component all mixing and the premature reaction between single component is prevented from.
Paper tinsel bag of the invention, the advantage is that it can be used in conventional and usually used pressurizing unit.
Paper tinsel bag is preferably suitable for use in the mixed adhesive based on dual cure multi-component adhesive system, particularly applies
The storage of the mixed adhesive described in EP10153243.
In preferred embodiments, paper tinsel bag of the invention still further comprises head, and in every kind of situation extremely
Few two receiving portions are used for an end of paper tinsel bag.Particularly, the thin bag with its associated end is not fixed on releasably
Head and therefore with it is permanently connected.Therefore, whole paper tinsel bag can be inserted readily on the acceptance division of pressurizing unit and therefrom
Remove.Advantageously, paper tinsel bag is fixed on head.For example, in application DE 102007000802 A1 and DE9100054 U1
Describe according to the usable head of the present invention.
The size of paper tinsel bag corresponds essentially to the size of the paper tinsel bag for dual component material, thus according to paper tinsel bag of the invention
The conventional pressurizing unit that can have been existed using in the market, mandatory necessary adjustment in the case of any of which.Depend on
The characteristic and needs of the material stored in paper tinsel bag, ratio can mutually provide in paper tinsel bag accordingly.
Composition on mixed adhesive, applies for EP10153243 with reference to disclosed in formerly, and its content is hereby incorporated into this Shen
Please in.
Explained by way of following EXPERIMENTAL EXAMPLE, the HV values of amine hardener are how many, the ratios of epoxides and amine, with
And the ratio of epoxides and vinyl esters can all influence mixing ratio, A1:A2≈3:1 will.
Embodiment
The composition of the first mixed adhesive is as follows, and wherein the mixed adhesive is based on first undocumented application
The embodiment 1 of EP101053243.
Following examples show that first, the HAV values of amine hardener are in mixing ratio A1:A2=3:It is important in 1 adjustment
Lever.By appropriate selection filler and the filling extent and mixing ratio of independent component K1, K2, embodiment 2 and 3 is set suitably to obtain
Obtain A1:A2=3:1.
According to the initial formula of application EP101053243
A) BADGE=bisphenol-As-diglycidyl ether
B) BDDMA=butanediols -1,4- dimethylacrylates
C) GlyMA=GMAs
d)A=2- methyl pentamethylene diamines (Invista)
e)C=tert butyl peroxy benzoates (AkzoNobel)
Embodiment 1
The composition of embodiment 1 corresponds to initial formula, and difference is to use density and 45g/ with 1g/L
The amine hardener of the HAV of val replacesA, and epoxides:Amine ratio reduction so that vinyl esters:Epoxidation
The ratio of thing is for about 1:1 (epoxy resin reduction by 20%).
1) for example from Hexion Specialty Chemicals companies3200 or3290
Embodiment 2
The composition of embodiment 1 corresponds to initial formula, and difference is, uses the density with 1g/L and 90g/val
The polyimide resin of HAV replacesEpoxides:Amine ratio reduction so that vinyl esters:The ratio of epoxides is for about 1:1 (ring
20%) oxygen tree fat reduced, and amine share increases by 20%, and (15%) in shortage is replaced to obtain slight amine excessive (20%).
1) for example from Hexion Specialty Chemicals companies3046 or3055
Embodiment 3
The composition of embodiment 1 corresponds to initial formula, and difference is, uses the density with 1g/L and 110g/val
The polyimide resin of HAV replacesEpoxides:Amine ratio reduction so that vinyl esters:The ratio of epoxides is for about 1:1 (ring
20%) oxygen tree fat reduced, and amine share increases by 20%, and (15%) in shortage is replaced to obtain slight amine excessive (20%).
1) for example from Hexion Specialty Chemicals companies3061 or3388。
Claims (10)
1. the bag of multi-component adhesive is used for, and it includes：
(I) resin Composition, it has：
The polymerizable compound of (a) at least one free radical,
(b) at least one compound polymerizable by addition polymerization,
(c) at least one accelerator,
(d) at least one inhibitor, and
(e) optionally at least a kind of compound with Liang Ge functional groups, wherein, a functional group can be with free radical (co) polymerization
And another functional group can by addition polymerization (co) polymerization, and
(II) curing agent component, it has
(A) at least one curing agent for addition polymerization, and
(B) at least one radical initiator,
The bag has
Part I A1, its at least three kinds single component for including multi-component adhesive,
Disconnect arrangement Part II A2, its at least two single component for including multi-component adhesive,
Wherein, the single component of multi-component adhesive is so divided into two parts A1 and A2 so that only mixed completely in single component
The reaction for the solidification of adhesive being carried out after conjunction and preventing between single component, it is characterised in that in Part I A1
At least following single component of multicomponent plaster system is provided in separate room K1 and K2, wherein the first Room K1 is included：
The polymerizable compound of (a) at least one free radical,
(d) at least one inhibitor, and
(e) optionally at least a kind of compound with Liang Ge functional groups, wherein, a functional group can be with free radical (co) polymerization
And another functional group can by addition polymerization (co) polymerization,
And second Room K2 is included：
(A) it is used for the curing agent of addition polymerization, and
(c) at least one accelerator.
2. bag according to claim 1, wherein Part I A1 is included：
The polymerizable compound of (a) at least one free radical,
(c) at least one accelerator,
(A) at least one curing agent for addition polymerization,
(d) at least one inhibitor, and
(e) optionally, at least one compound with Liang Ge functional groups, wherein, functional group can be (common) poly- with free radical
Close and another functional group can be included by addition polymerization (co) polymerization, and Part II A2：
(b) at least one compound polymerizable by addition polymerization, and
(B) at least one radical initiator.
3. bag according to claim 1, the first Room K1 of wherein Part I A1 is further used for comprising at least more than a kind of
The reactive diluent of the polymerizable compound of free radical.
4. bag according to claim 1, the mixing ratio A1 of wherein Part I A1 and Part II A2:A2 is 1:1 to 10:1
Between.
5. the bag of claim 4, the mixing ratio A1:A2 is 3:1 or 5:1.
6. according to the bag of any one of preceding claims, wherein the mixing ratio of the first Room K1 and second Room K2 is 4:1 to 1:4.
7. bag according to claim 6, wherein the mixing ratio of the first Room K1 and second Room K2 is 4:1 to 1:1.
8. bag according to claim 1, wherein at least one is epoxy compound by the polymerizable compound (b) of addition polymerization
Thing, at least one curing agent (A) for addition polymerization is amine, and optionally, the compound (e) with Liang Ge functional groups is it
In the functional group chemical combination with Liang Ge functional groups that can be epoxide group with free radical (co) polymerization and another functional group
Thing.
9. bag according to claim 1, it is characterised in that the bag is the paper tinsel bag with the first paper tinsel bag Fb1 and the second paper tinsel bag Fb2.
10. bag according to claim 9, it is characterised in that wrapped in paper tinsel and further provide for having for paper tinsel each end of bag
The head of at least two receiving portions.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102012219480.0 | 2012-10-24 | ||
| DE102012219480.0A DE102012219480A1 (en) | 2012-10-24 | 2012-10-24 | Packaging for multi-component binder systems |
| PCT/EP2013/072035 WO2014064084A1 (en) | 2012-10-24 | 2013-10-22 | Packaging for multi-component adhesive system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104822641A CN104822641A (en) | 2015-08-05 |
| CN104822641B true CN104822641B (en) | 2017-06-23 |
Family
ID=49474410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380062470.4A Expired - Fee Related CN104822641B (en) | 2012-10-24 | 2013-10-22 | For the bag of multi-component adhesive system |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9914578B2 (en) |
| EP (1) | EP2911996B1 (en) |
| JP (1) | JP2016500737A (en) |
| CN (1) | CN104822641B (en) |
| CA (1) | CA2889285A1 (en) |
| DE (1) | DE102012219480A1 (en) |
| ES (1) | ES2674350T3 (en) |
| WO (1) | WO2014064084A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102012219479B4 (en) * | 2012-10-24 | 2016-12-15 | Hilti Aktiengesellschaft | Reaction resin composition and its use |
| JP6447557B2 (en) * | 2016-03-24 | 2019-01-09 | 日亜化学工業株式会社 | Method for manufacturing light emitting device |
| EP3838862A1 (en) * | 2019-12-18 | 2021-06-23 | Hilti Aktiengesellschaft | Use of a reactive resin composition for chemical attachment of an anchoring means in a hole |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190458A (en) * | 2010-02-11 | 2011-09-21 | 喜利得股份公司 | Resin mortar suitable for construction purposes, especially for chemical anchoring |
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| GB1352063A (en) | 1971-01-08 | 1974-05-15 | Ici Ltd | Polymerisable compositions and resins derived thererom |
| US3782600A (en) * | 1972-06-13 | 1974-01-01 | Borden Inc | Co-dispenser applicator and spatula cap |
| US4618658A (en) | 1985-05-16 | 1986-10-21 | The Dow Chemical Company | Polymer modified epoxy resin compositions |
| DE3744390A1 (en) | 1987-12-29 | 1989-07-13 | Basf Ag | Fibre composite materials based on modified vinyl ester urethane resins |
| GB8810299D0 (en) | 1988-04-29 | 1988-06-02 | Scott Bader Co | Vinyl terminated urethane containing resins |
| US5083674A (en) * | 1989-06-21 | 1992-01-28 | Power Poxy, Inc. | Container for epoxy adhesives and the like |
| DE9100054U1 (en) | 1991-01-04 | 1991-04-11 | Cocon Kunststoffen B.V., Arkel | Storage pack for two-component polyurethane material |
| DE4131457A1 (en) | 1991-09-21 | 1993-03-25 | Basf Ag | CARTRIDGE OR CARTRIDGE FOR CHEMICAL FASTENING TECHNOLOGY |
| US5333737A (en) * | 1992-08-19 | 1994-08-02 | Power Poxy Adhesives, Inc. | Packaging system for two part epoxy adhesives and the like |
| US5287961A (en) * | 1992-10-23 | 1994-02-22 | W.R. Grace & Co.-Conn. | Multi-compartment package having improved partition strip |
| DE4304620A1 (en) * | 1993-02-16 | 1994-08-18 | Fischer Artur Werke Gmbh | anchoring cartridge |
| DE4304824A1 (en) * | 1993-02-17 | 1994-08-18 | Upat Max Langensiepen Kg | Reaction resin mortar for two-component systems |
| DE19531649A1 (en) | 1995-08-29 | 1997-03-06 | Basf Ag | Dowel compound for chemical fastening technology |
| GB9523230D0 (en) * | 1995-11-14 | 1996-01-17 | Courtaulds Packaging Ltd | A two-compartment container |
| DE19618693A1 (en) * | 1996-05-09 | 1997-11-13 | Upat Max Langensiepen Kg | Cartridge for interchangeable twin component masses in foil bags |
| EP1225189A1 (en) * | 2000-12-22 | 2002-07-24 | Dsm N.V. | Two-component chemical fastening systems |
| US6520335B2 (en) * | 2001-02-20 | 2003-02-18 | Daniel E. Moran | Method and container for packaging multi-component polymer coatings and adhesives |
| WO2007109915A1 (en) * | 2006-03-24 | 2007-10-04 | Medmix Systems Ag | Discharge arrangement with detachably fastenable accessory parts |
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2012
- 2012-10-24 DE DE102012219480.0A patent/DE102012219480A1/en not_active Ceased
-
2013
- 2013-10-22 CA CA2889285A patent/CA2889285A1/en not_active Abandoned
- 2013-10-22 WO PCT/EP2013/072035 patent/WO2014064084A1/en active Application Filing
- 2013-10-22 EP EP13780131.2A patent/EP2911996B1/en active Active
- 2013-10-22 ES ES13780131.2T patent/ES2674350T3/en active Active
- 2013-10-22 CN CN201380062470.4A patent/CN104822641B/en not_active Expired - Fee Related
- 2013-10-22 JP JP2015538406A patent/JP2016500737A/en active Pending
-
2015
- 2015-04-24 US US14/695,851 patent/US9914578B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190458A (en) * | 2010-02-11 | 2011-09-21 | 喜利得股份公司 | Resin mortar suitable for construction purposes, especially for chemical anchoring |
Also Published As
| Publication number | Publication date |
|---|---|
| US9914578B2 (en) | 2018-03-13 |
| CN104822641A (en) | 2015-08-05 |
| EP2911996A1 (en) | 2015-09-02 |
| WO2014064084A1 (en) | 2014-05-01 |
| DE102012219480A1 (en) | 2014-05-15 |
| US20150232253A1 (en) | 2015-08-20 |
| JP2016500737A (en) | 2016-01-14 |
| ES2674350T3 (en) | 2018-06-29 |
| CA2889285A1 (en) | 2014-05-01 |
| EP2911996B1 (en) | 2018-03-21 |
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